Chromite refractory materials



: llNI TED "STA E fractory of a stabilized chrome ore and] dead Patented Jan l4, 1936" s. ATE T OFFICE 'cnnom'm amac'ronr MATERIALS v Gilbert E. Sell, 'Conshohocken. 2a., asslgnor to E. J. Lavino and Company, Philadelphia, Pa., a corporation of Delaware No Drawing.

8 Claims. (01. 106-9) 7 My invention relates to a novel refractory material, and more particularly it relates to a chromite refractory of improved physical and ,chemical characteristics. The method described 'in this application ls the subject matter of a -co-pending application Serial No. 53,076, filed December 5, 1935 as a division of this application.

The principal object of the present invention in is to provide a chromite refractory in which the physical and chemical properties are improved in a marked manner and in which the disadvantages accompanyin chromite refracto- 1188 heretofore manufactured have been over- Come.

One of the objects of my invention is to provide a chromite refractory whose softening point is materially higher than that of similar refractorles of the prior art, with the accompanying result that the refractory will not deform at any usual furnace temperatures or under any furnace conditions encountered'in theme of the product, regardless of the severity. thereof.

A further object of the invention is to furnish 5 a chromite refractory material which possesses a minimum tendency to spall and has a very low thermal conductivity and a low coeflicient of expansion. I 3

Still another, object of my invention is to provides. chromite refractory which is neutral chemically and in which the bond is much less active from a' chemical standpoint than heretofore, whereby the slagging action is much less and a higher temperature can be employed before reaction starts.

The present invention in its preferable form contemplates the combination in achromite reburnt-crystallized oxide, for exsi nie, periclas. in such proportion that the low inciting point gangue of the'chrome ore, comprising magnesium silicates of -a lower average magnesium oxide content than forsterite, is converted by the magnesium oxide into magnesium-silicate of high melting point, knownas forsterite". Hereinafter the' term perlclaseiwill "beused throughout, and it is to be understood that within that term is included an oxide having the physical characteristics of 'regardless'of its name-on-somce chromeoreandthetwamatenalsmaybesublama mentz.

p n. i

totherawchromeoreandthetwomaterlals may be subjected to the preliminary stabilizing heat treatment, and the remainder of the periclase may then be added to the ground heat- 0 treated ore in the tempering operation; and 5 III. All of the periclase may be added to the heat-treated stabilized chrome ore duringthe tempering operation.

rounding the particles of chromite. Y

In my co-pending application, Serial No. 540,-

' 495, flied May 27, 1931, for Refractory materials and method of making the same of which the present application is acontinuation in part, it

- there is described the stabilization of raw chrome ore by the heat treatment thereof. As there pointed out, raw chrome ore contains many impurities which togethei with the chromite, un-

less the chrome ore is stabilized, undergo reac- 20 tions and. molecular rearrangements and physical changes during the burningof the preformed brlcks'or other shaped articles. The results obtained in the manufacture of chromite refrac torles from raw chrome ore, therefore, are for- 25 tuitous, shrinkage often occurring during the burning which results fin deformation of the products and fractures thereof. 1

This is also evidenced by changes in the physical constants of the material, for example, in 30 changes in the specific gravity and specific heat. It is, therefore,desirable preliminarily to'heattreat-the chrome ore so that the constituents will be in the physical and chemical condition found at the burning temperature, thus preclud- 35 ing physical and chemical rearrangements dirring burning which cause deformation and. frac-. tures. The heat treatment also results in a very definite migration of the gangue materlala'and after such treatment the gangue will be found surrounding the surfaces of the particles of chromite. The stabilization temperature should not be-less than the temperature to which the preformed refractory body is subjected in burning. for example, 3,000 degrees I". to 3,400 degrees R, 45 depending on theore being treated. The heat treatment is continued until the desired rear- .rangementafsuch as the recrystallization of the spine! and the redistribution of the sangue have-taken place.

In'the actiire of the refractories of the'- present invention it is also advisable to subject ,the rawchr'ome ore to a similar stabilizing heat l treatmentprior to the tempering, pressing and burning. operations. The stabilization process ;removes the ahrlnkage from the material, and;

th s-illuminates from the the diiiicultles encounteredin, theuse ofraw ore and rain to a the number of' iect's. rm

llminaryheattreatmentalsofpresentsthe p for reaction with the periclase in the most available condition, whether the periclase is added before the heat treatment, or during the tempering operation. If for the sake of economy, or for other reasons, it is desired to employ crude chrome ore without prestabilization or heattreatment, the raw untreated ore may be used and the process carried on in the manner here- I inafter described. The properties of the product will'be more difilcult to control and the process will not result in as high a yield of satisfactory usable products. It is for these reasons that the prestabilization of the ore is recommended.

Raw chrome ore is'a two-component system from a refractory standpoint. The first com-v ponent comprises 70% to 90% of chromite known as chromite spinel which is a mineral, the basic radicles are FeO and MgO in varying .amounts, but the sum of which bears a constant molecular'relationship to the sum of the acid radicles CH0: and A1201. The second component known as gangue consists of MgO and S10. which are chemically combined as one of the magnesium silicates, but are combined in vary- F. to 2,600 degrees F., depending upon the ratio ing proportions molecularly. The lowest magnesium silicate is (MgOh (SiOJa; while the highest one that normally occurs associated with the chrome ore is MgO $10,. This second component is rarely pure and contains as impurities Feioa, CaO,Al,O., S101, etc. The melting point of these gangue materials is from 2,300 degrees of MgO to SiOz and the percentage of impurities present. The present invention contemplates the addition of periclase to the chrome ore, whereby a reaction is brought about between the periclase and the magnesium silicates, with the result that the low melting point magnesium silicates are converted into a refractory body of high melting point, known as forsterite, whose formula is (MgO)2.SiO2. The melting point of the forsterite is approximately 3,500 degrees F. in a purestate, but in'the presence of an excess of magnesium oxide, the fusion of the compound is not,

complete at 3,700 degrees F. Both the temperatures of 3,500 and 3,700 degrees F. are in excess of those encountered in the use of the refractory materials. As previously stated by the term periclase-is included any dead burnt crystallized magnesium oxide, and for practical purposes, commercial periclase containing from 90% to 93% magnesium oxide is employed. The magnesium oxide employed must be a dead burnt material, for otherwise hydrolysis occurs which causes an increase in the volume of the brick andalso results in the liberation of steam at a high rate, due to the fact that the magnesium oxide resulting from the hydrolysis decomposes at a definite temperature. The liberation of the steam creates a pressure within the preformed sents noneof the stated difliculties, since the hydrolysis of this type of compound at a very slow rate.

The amount of dead burnt magnesium oxide takes place (periclase) employed is determined by chemical y the ore and the molecular ratiosof magnesium oxide to silicon dioxide combined in the magnesium silicates may beknown. The amount of periclase added in the preferable instance is dependent upon the amount required to convert the magnesium silicates and free silica found to be present in the ore to forsterite without decomposition of the chromite spinel of the ore, and in general, in order to obtain the best results an excess of periclase over that required is employed in order to insure that after the reaction no free pared to prior products is obtained, the improved properties being proportional to the amount of forsterite formed. In most instances the proportion added will be between 17% and 25% of the weight of the chrome ore and while the upper limit of periclase addition is not critical and considerable excess can be added without detriment, it must not be added in such amount as will result in the formation of appreciable quantity of water-soluble magnesium chromate. The presence of magnesium chromate in the refractory is a direct indication of the upper limit of periclase addition which is permissible.

The raw mix of treated chrome ore and 'periclase, regardless of which of the three methods previously outlinedare employed in its preparation, is screened to suitable size and is tempered according to any well known method in the presence of plasticizers and binders, if desired. The tempered material then is pressed, for example, either in a lever or an hydraulic press, as has previously been employed in the manufacture of similar refractories. The pressure in the press may vary widely, for instance, a pressure of 600 pounds per square inch, or higher, may be employed, depending upon the shape, size and porosity required. The refractory is burned by any known method, for example, in a tunnel kiln with a controlled time and temperature curve, both for heating and cooling. The burning temperature is preferably higher than that employed in the manufacture of the usual chromite refractories, and in fact a buming temperature of about 3,000 degrees F. which corresponds to cone 28 completely down is particularly suitable.

In a typical case, crude chromeore is employed whose primarymineral is chromite and whose secondary mineral is one or more of themembers of the serpentine family, and whose chemical analysis is as follows:

. Percent CIzOv v 42.0 to 45.0 S109 9.5 vt0 10.00 ieO 13.0 to 16.0 A1201 11.0 to 14.0 09.0 1.0 or less MgO 12.0 to 15.0

It willjbe noted that the ore contains approximately 10% of silica, and in orde'rto' determine the amount of periclase to be added, if only approximate figures are desired, it may be assumed that the given amount of silica will require magnesium oxide in the ratio of two parts of magnesium oxide to one part of silica to form forsterite ((MgO)2.SiO2). A calculation taking thirteen parts of magnesium oxide are required.

However, aspreviously pointedout. it is desirable to employ an excess of magnesium oxide in order to insure that all of the silica either free or combined as magnesium silicate will be converted into forsterite, and experiments have shown. that with an ore of the above analysis 10- '22%% of pericla'se containing 92% of magne slum oxide gives the best, results.

If method .1 is to be employed in which all the 'periclase is addedto the untreated ore and the mixture subjected to the heat treatment emciflcally at temperatures between 3200 F. and

3400 F. The best results are obtained by increasing the temperature very quickly from just .below the melting point of the lowest melting point magnesium silicate up to the desired temperature, say 3200 -F., in order to get a very mobile liquid to react with thepericlase. The time required varies inversely with the temperature,

and the briquetsare subjected to the stabilization temperature for a sufficient time to convert the magnesium silicata and silica into forsterite and to allow the chemical and molecular changes and rearrangements to take place-in the chrome cm. The resulting product isa two-wmp'onent body, both components of which have a high melting point, and a microscopic examination 7 shows that the pericla'se is found in'a thin film surrounding the chromite particles.

After the heat treatment, two separate grinds are prepared which will be termed herein grind A" and grind B. The screens hereinafter discussed are all of the dimensions adopted by' the of Standards. Grind A is a so-called rolledproduct and is sized with one screen, everything that passes through a 6 mesh screen being employed. A screen analysis shows that of the material that passes through the 6 mesh screen, not less 85% are caught on a 40 mesh screen, the remainder through.

The particles are flat faced, sharp, and pointed,

and are of three approximately equal dimensions, M

- without rounded corners. Grind Bis a pulverized material made in a rubbing mill which res'ults in round cornered particles of nearly spherical shape. All ofthe particles pass through a zo-meshscreen and at least 50% pass through a 200 mesh screen, although in the most preferred case, through said=screen.'

17% parts of grind A by weight and. 22% parts ofgrind B by weight are placed in a tempering panto which is added 1% 0! 800180, 25%01 boiled starch prepared by addlngborax to starch and subsequently heating the mixture, and 2% ofanoil such as. fuel oil. Water-is added to the mixture in proportions sumcient to give the necessaryplastlcitytothemassduringtheii operation.- For example, the moisture content may be brought up by the addition of water to about 4% of the weight of the ore. Thematerial istreated in the tempering pan until it is which requires onlyhire or ten minutes. It isdesirable to treat thematerialinthepansothat'itianotfurther aosaoie into'consideration the molecular weights of the compounds, therefore, shows that fl-pproxhnately ground and the stirring may be rubbercovered and of relatively light weight to insure this. There must, however-,be interstitial flow between the particles so that a homogeneous mixis obtained. After the tempe pressed to the desired shape, in any desired manner, such asin a lever or hydraulic press with a pressure of 600 pounds ,themassis by any known method, for example, b a. the shaped material through a tunnel kiln with a controlled time and temperature curve both for heating'and cooling.

Preferably a'ninety hour cycle is used through the tunnel which may be 327 feet long of which '85 feet in the center is the actual flre zone. The

temperature of 'thefurnace at the beginning of the fire zone is in the neighborhood of 2200 F. and reaches its peak at 8000" F. or higher.

The material remains in the fire zone for ap-. proximately twenty-four hours.

If method 2 is to be employed, thedesiredamount of periclase is added to the raw crude 25 jected tothe stabilizing heat-treatment sis set, forth above under the discussion of method 1.

ore, for example 10%, and the mixture is sub- After the stabilization step, the remaining periclase necessary to make up the total amount re quired is ground with sufficient heat-treated and po os y per square inchor higher, depending upon the size, shape. nd porosity required. The burning 10 isaccomp are to makeup 22 oi the totalr nix' in such a manner as to give a'grind of the characteris- 'tlc of grind B. 775 partsof grindfA made up of treated ore and the 22 parts of grind B are added to the tempering process of making the refractory material thereafter. may be'carried out in the same manner as dey scribed-in connection with method 1.

If method 3 is to be employed, the crudeore is subjected to thestabilizing. heat-treatment as previously described without the addition of any periclase and is ground after such treatment intheformof grindA. Thepericlaseisground to' constitute grind B, and 77% parts of grind A and 22 parts of'grindB are added to'the tempering pan and the process is thereafter carried outin the same manner described.

In all of these methods, the low melting point gangue has been converted into a refractory materiaL'forsterite', which is spread as a thin him the mass of oreso that it can'be reacted upon by the 'perlclase whether. that compound is added during" or after the heat-treatment. The distribution is such that the reaction can be carried out during the burning'as in methods2 and 3 without any physical distortion or dis- ()hromite refractories previously manufactured have a softening point between 2300' r. and 2600' F. and, deform at these temperatures under a load of. inch.- They also shrink verybadly at 2600" F. and sag under their own weight at this temperature. If submittedtoaspallingtestahighspallinglosswill as previously over the chromite particles. The stabilizing heat-treatment distributes the gangue through be encountered. Thebond is also active chemicallyand slagging tends to occur at the temperatures employed in the furnaces. In contradistinction to these properties, the chromite brick of the present invention does not soften at 3500. F. and. therefore, does not deform or sag at any furnace temperature or under any furpace conditions under 3500' I". orhigher. The 7 1 brick has, a minimum tendency to spalland t the bond is practically inactive chemically and,

therefore, no diiiiculty is encountered with slagging, it being possible to carry the refractory to much higher temperatures than previously before reaction starts. The new brick is neutral chemically and has a very low thermal conductivity and a low coeificient of expansion. The low thermal conductivity is evidenced by the fact that nine inches of the refractory of the present invention will allow less heat to pass than eighteen inches of a silica refractory.

Considerable modification is possible in the percentage of dead burnt magnesium oxide added, as well as in the methods employed in stabilizing the crude chrome ore and in the manforsterite. v

2. The productjofclaim 1 in which the forsterite surrounds the chromite spinel in the form of a thin film.

3. A shaped burned chromite refractory consisting of a mass of adhering undecomposed I substantially of undecomposed recrystallized chromite spinel with magnesium silicate compounds in the form of forsterite.

6. The product of claim 5 in which the forsterite surrounds the recrystallized chromite spinel particles in the form of a thin film.

'7. A burned chromite refractory material consisting of a mass of adhering undecomposed recrystallized chromite spinel particles, substantially all of the magnesium silicate compounds associated therewith being present in the form of forsterite.

8. The product of claim 7- in which the forsterite surrounds the recrystallized chromite spinel particles in the form of a thin film.

GILBERT E. SEIL. 

